Surface Heparinization of a Magnesium-Based Alloy: A Comparison Study of Aminopropyltriethoxysilane (APTES) and Polyamidoamine (PAMAM) Dendrimers

Abstract

Magnesium (Mg)-based alloys are biodegradable metallic biomaterials that show promise in minimizing the risks of permanent metallic implants. However, their clinical applications are restricted due to their rapid in vivo degradation and low surface hemocompatibilities. Surface modifications are critically important for controlling the corrosion rates of Mg-based alloys and improving their hemocompatibilities. In the present study, two heparinization methods were developed to simultaneously increase the corrosion resistance and hemocompatibility of the AZ31 Mg alloy. In the first method, the surface of the AZ31 alloy was modified by alkali–heat treatment and then aminolyzed by 3-amino propyltriethoxy silane (APTES), a self-assembly molecule, and heparin was grafted onto the aminolyzed surface. In the second method, before heparinization, polyamidoamine dendrimers (PAMAM4-4) were grafted onto the aminolyzed surface with APTES to increase the number of surface functional groups, and heparinization was subsequently performed. The presence of a peak with a wavelength of about 1560 cm−1 in the FTIR spectrum for the sample modified with APTES and dendrimers indicated aminolysis of the surface. The results indicated that the corrosion resistance of the Mg alloy was significantly improved as a result of the formation of a passive layer following the alkali–heat treatment. The results obtained from a potentiodynamic polarization (PDP) test showed that the corrosion current in the uncoated sample decreased from 25 µA to 3.7 µA in the alkali–heat-treated sample. The corrosion current density was reduced by 14 and 50 times in samples treated with the self-assembly molecules, APTES and dendrimers, respectively. After heparinization, the clotting time for pristine Mg was greatly improved. Clotting time increased from 480 s for the pristine Mg sample to 630 s for the APTES- and heparin-modified samples and to 715 s for the PAMAM- and heparin-modified samples. Cell culture data showed a slight improvement in the cell-supporting behavior of the modified samples.